Method of manufacturing semiconductor device

ABSTRACT

The method of manufacturing a semiconductor device according to the present invention includes: an insulating layer forming step of forming an insulating layer made of an insulating material containing Si and O; a groove forming step of forming a groove in the insulating layer; a metal film applying step of covering the inner surface of the groove with a metal film made of MnO x  (x: a number greater than zero) by sputtering; and a wire forming step of forming a Cu wire made of a metallic material mainly composed of Cu on the metal film.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of manufacturing asemiconductor device having a Cu wire made of a metallic material mainlycomposed of Cu (copper).

2. Description of Related Art

In a highly integrated semiconductor device, Cu having higherconductivity than Al (aluminum) maybe employed as the material for awire. A wire (a Cu wire) employing Cu as the material therefor isembedded in a fine groove formed in an insulating layer on asemiconductor substrate by a damascene process, since it is difficult tofinely pattern Cu by dry etching.

In general, SiO₂ (silicon oxide) is employed as the material for theinsulating layer. However, Cu has high diffusibility into SiO₂. When theinner surface of the groove formed in the insulating layer made of SiO₂and the Cu wire are directly in contact with each other, therefore, Cudiffuses into the insulating layer, to reduce the dielectric voltage ofthe insulating layer. Therefore, a barrier film for preventing Cu fromdiffusing into the insulating layer must be provided between theinsulating layer and the Cu wire.

A self-formation process employing an alloy material (hereinafter simplyreferred to as a “CuMn alloy”) containing Cu and Mn (manganese) is knownas a technique of forming the barrier film. In the self-formationprocess, an alloy film made of the CuMn alloy is formed on the surfaceof the insulating layer including the inner surface of the groove bysputtering. Then, a Cu layer made of a metallic material mainly composedof Cu is stacked on the alloy film by plating. Thereafter heat treatmentis performed, whereby Mn contained in the alloy film is bonded to Si(silicon) and O (oxygen) contained in the insulating layer, and abarrier film made of Mn_(x)Si_(y)O_(z) (x, y and z: numbers greater thanzero. Mn_(x)Si_(y)O_(z) is hereinafter simply referred to as “MnSiO”) isformed on the inner surface of the groove.

After the formation of the barrier film, the surface of the Cu layer ispolished by CMP (Chemical Mechanical Polishing) until the same is flushwith the surface of the insulating layer out of the groove. Thus, a Cuwire embedded in the groove through the barrier film is obtained.

Excess Mn not contributing to the formation of the barrier film (bondingto Si and O) diffuses into the Cu layer. If the quantity of Mn diffusinginto the Cu layer is large, Mn remains in the Cu wire, to increase theresistance of the Cu wire. While the specific resistance of pure Cu isabout 1.9 to 2.0 μΩ.cm, the specific resistance of Cu containing Mn by1% (at. %) in atomicity is about 5 to 6 μΩ.cm. In a fine Cu wire havinga width of 60 to 70 nm, slight increase in specific resistance leads toremarkable increase in wire resistance.

In order to reduce the quantity of Mn remaining in the Cu wire, thealloy film made of the CuMn alloy may be set to the minimum thicknessnecessary for forming the barrier film.

When the alloy film is formed by sputtering, however, the CuMn alloy isharder to bond to the side surfaces of the groove as compared with thebottom surface thereof. If the alloy film is formed to have the minimumthickness necessary for forming the barrier film on the bottom surfaceof the groove, therefore, portions of the alloy film formed on the sidesurfaces of the groove are excessively reduced in thickness.Adhesiveness of the CuMn alloy to SiO₂ is not high, and hence theadhesiveness between the alloy film and the side surfaces of the groovemay be reduced to result in separation of the alloy film from the sidesurfaces of the groove if the alloy film is excessively reduced inthickness on the side surfaces of the groove. When the alloy filmseparates from the side surfaces of the groove, the barrier film made ofMnSiO cannot be excellently formed on the separating portions.

Therefore, the alloy film is formed with a thickness larger than theminimum thickness necessary for forming the barrier film, in order toensure the adhesiveness of the alloy film to the inner surface of thegroove and prevent separation of the alloy film from the side surfacesof the groove. The adhesiveness of the CuMn alloy to SiO₂ is reduced asthe Mn concentration therein is decreased, and hence a CuMn alloy havinga relatively high Mn concentration is employed as the material for thealloy film. Therefore, the alloy film excessively contains Mn.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a method ofmanufacturing a semiconductor device capable of reducing the quantity ofMn remaining in a Cu wire.

A method of manufacturing a semiconductor device according to a firstaspect of the present invention includes: an insulating layer formingstep of forming an insulating layer made of an insulating materialcontaining Si and O; a groove forming step of forming a groove in theinsulating layer; a metal film applying step of covering the innersurface of the groove with a metal film made of MnO_(x) (x: a numbergreater than zero) by sputtering; and a wire forming step of forming aCu wire made of a metallic material mainly composed of Cu on the metalfilm.

According to the method, the groove is first formed in the insulatinglayer made of the insulating material containing Si and O. Then, theinner surface of the groove (the side surface and the bottom surface ofthe groove when the groove is concavely formed) is covered with themetal film made of MnO_(x) (x: a number greater than zero, MnO_(x) ishereinafter simply referred to as “MnO”) by sputtering. At this time,MnO in the metal film is introduced into the inner surface of thegroove, i.e., a portion of the insulating layer facing the groove, dueto the energy of the sputtering. Thus, Si and O in the insulating layerand MnO in the metal film are bonded to one another, and a barrier filmmade of MnSiO is formed on the inner surface of the groove. Thereafterthe Cu wire made of the metallic material mainly composed of Cu isformed on the metal film (the barrier film).

MnO has higher adhesiveness to the insulating material containing Si andO as compared with the CuMn alloy. Therefore, the metal film made of MnOhardly separates from the side surface of the groove, also when the sameis formed with a small thickness (the minimum thickness necessary forforming the barrier film) necessary and sufficient for forming thebarrier film with a desired thickness. Therefore, the barrier film canbe excellently formed on the inner surface of the groove. When the innersurface of the groove is covered with the metal film, the barrier filmmade of MnSiO can be formed due to the energy of the sputtering, wherebyno heat treatment may be performed for forming the barrier film.

The metal film is formed with such a small thickness, whereby thequantity of excess Mn not contributing to the formation of the barrierfilm can be reduced. Thus, the quantity of Mn remaining in the Cu wireformed on the barrier film can be reduced.

Therefore, the quantity of Mn remaining in the Cu wire can be reducedwhile the barrier film can be excellently formed on the inner surface ofthe groove.

A lower wire electrically connected with the Cu wire may be formed underthe insulating layer. In this case, the lower wire and the Cu wire canbe electrically connected with each other by carrying out a via holeforming step of forming a via hole extending from the groove toward thelower wire and passing through the insulating layer in the thicknessdirection after the groove forming step and before the metal filmapplying step and carrying out a via forming step of forming a via madeof a metallic material mainly composed of Cu in the via hole after themetal film applying step. In the metal film applying step, the barrierfilm made of MnSiO can be formed on the side surface of the via hole bycovering the side surface of the via hole and a portion of the surfaceof the lower wire facing the via hole with the metal film in addition tothe inner surface of the groove.

MnO employed as the material for the metal film has higher electricalresistance as compared with Cu. When the metal film made of MnO ispresent on the portion of the surface of the lower wire facing the viahole, therefore, the electrical resistance between the via and the lowerwire is increased.

Therefore, a step of removing O from a portion of the metal film incontact with the surface of the lower wire by hydrogen reduction ispreferably carried out in advance of the via forming step. When O isremoved, MnO is reduced to Mn. Mn diffuses into the via and the like,whereby the metal film disappears from the lower wire.

In place of the step, a step of selectively removing a portion of themetal film in contact with the surface of the lower wire by reversesputtering may be carried out in advance of the via forming step. Thereverse sputtering can be performed in a sputtering apparatus identicalto that employed for the sputtering. When the reverse sputtering isemployed in the step of removing the portion of the metal film incontact with the surface of the lower wire, therefore, the step ofpartially removing the metal film can be carried out continuously to themetal film applying step in the same sputtering apparatus. When the Cuwire is formed by plating, a seed film is formed on the metal film bysputtering. In the case, the step of forming the seed film can becontinuously carried out in the same sputtering apparatus, in additionto the metal film applying step and the step of partially removing themetal film. Therefore, the structure of an apparatus for manufacturingthe semiconductor device can be simplified and a semiconductor wafer (asemiconductor substrate in a wafer state provided with the insulatinglayer) may not be transported between the steps, whereby the timenecessary for manufacturing the semiconductor device can be reduced.

The wire forming step may include the steps of forming a seed film madeof a metallic material mainly composed of Cu on the metal film bysputtering, and forming a plating layer made of Cu on the seed film byplating.

However, the plating layer has a heterogeneous crystal structure andhigh specific resistance in the state grown by plating. If the Cu wireand the via are formed by plating, therefore, the wire forming steppreferably includes a crystallizing step of crystallizing the platinglayer by heat treatment. Thus, the crystal structure of the platinglayer is homogenized (crystallized), whereby the specific resistance ofthe Cu wire and the via consisting of the plating layer can be reduced.

A method of manufacturing a semiconductor device according to a secondaspect of the present invention includes: a groove forming step offorming a groove in an insulating layer made of an insulating materialcontaining Si and O; a metal film applying step of covering the innersurface of the groove with a metal film made of Mn; a barrier filmforming step of forming a barrier film made of MnSiO on the innersurface of the groove by heat treatment after the metal film applyingstep; and a wire forming step of forming a Cu wire made of a metallicmaterial mainly composed of Cu on the barrier film.

According to the method, the groove is first formed in the insulatinglayer made of the insulating material containing Si and O. Then, theinner surface of the groove (the side surface and the bottom surface ofthe groove when the groove is concavely formed) is covered with themetal film made of Mn. Then, the heat treatment for bonding Mn in themetal film and Si and O in the insulating layer to one another isperformed. As a result of the heat treatment, the barrier film made ofMnSiO is formed on the inner surface of the groove. Thereafter the Cuwire made of the metallic material mainly composed of Cu is formed onthe barrier film.

Mn has higher adhesiveness to the insulating material containing Si andO as compared with the CuMn alloy. Therefore, the metal film made of Mnhardly separates from the side surface of the groove also when the sameis formed with a small thickness (the minimum thickness necessary forforming the barrier film) necessary and sufficient for forming thebarrier film with a desired thickness. Therefore, the barrier film canbe excellently formed on the inner surface of the groove.

The metal film is formed with such a small thickness, whereby thequantity of excess Mn not contributing to the formation of the barrierfilm can be reduced. Thus, the quantity of Mn remaining in the Cu wireformed on the barrier film can be reduced.

Therefore, the quantity of Mn remaining in the Cu wire can be reducedwhile the barrier film can be excellently formed on the inner surface ofthe groove.

The barrier film made of MnSiO may be formed by a method of covering theinner surface of the groove with an alloy film made of a CuMn alloy andbonding Mn in the alloy film and Si and O in the insulating layer to oneanother by heat treatment thereby forming the barrier film on the innersurface of the groove. Alternatively, the barrier film may be formed bya method of covering the inner surface of the groove with a metal filmmade of Mn, forming a thin film (a seed film employed for growing Cu byplating, for example) made of Cu on the metal film and thereafterforming the barrier film on the inner surface of the groove by heattreatment.

According to either method, however, Cu spherically aggregates on thebarrier film in the heat treatment. If spherically aggregating on thebarrier film, Cu cannot be excellently grown on the barrier film byplating when the Cu wire is formed by plating.

In the method according to the second aspect, on the other hand, Cu isnot present on and in the metal film made of Mn in the formation of thebarrier film, whereby no Cu spherically aggregates on the barrier film.Therefore, Cu can be excellently grown on the barrier film by plating.

The wire forming step may include the steps of forming a seed film madeof a metallic material mainly composed of Cu on the metal film bysputtering, and forming a plating layer made of Cu on the seed film byplating. No spherically aggregating Cu is present on the barrier film,and hence the seed film can be excellently formed on the barrier film,and the plating layer can be excellently formed on the seed film.

However, the plating layer has a heterogeneous crystal structure andhigh specific resistance in the state grown by plating. If the Cu wireis formed by plating, therefore, the wire forming step preferablyincludes a crystallizing step of crystallizing the plating layer by heattreatment. Thus, the crystal structure of the plating layer ishomogenized (crystallized), whereby the specific resistance of the Cuwire consisting of the plating layer can be reduced.

A method of manufacturing a semiconductor device according to a thirdaspect of the present invention includes the steps of: forming a groovein an insulating layer made of an insulating material containing Si andO; covering the inner surface of the groove with an alloy film made of aCuMn alloy; stacking a Cu layer made of a metallic material mainlycomposed of Cu on the alloy film to fill up the groove; forming abarrier film made of MnSiO between the Cu layer and the insulating layerby heat treatment; stacking a sacrificial layer made of an insulatingmaterial containing Si and O on the Cu layer for forming a reactionproduct film made of MnSiO on the Cu layer after the formation of thebarrier film; and removing the sacrificial layer and the reactionproduct film from the Cu layer.

According to the method, the groove is first formed in the insulatinglayer made of the insulating material containing Si and O. Then, theinner surface (the side surface and the bottom surface) of the groove iscovered with the alloy film made of the CuMn alloy. Thereafter the Culayer made of the metallic material mainly composed of Cu is formed onthe alloy film to fill up the groove. After the formation of the Culayer, the barrier film made of MnSiO is formed between the Cu layer andthe insulating layer by heat treatment. After the formation of thebarrier film, the sacrificial layer made of the insulating materialcontaining Si and O is stacked on the Cu layer.

The sacrificial layer contains Si and O, whereby Si and O contained inthe sacrificial layer and Mn contained in the Cu layer are bonded to oneanother on the interface between the Cu layer and the sacrificial layerwhen heat is applied to the Cu layer and the sacrificial layer, to formthe reaction product film made of MnSiO. After the formation of thereaction product film, the sacrificial layer and the reaction productfilm are removed from the Cu layer. After the removal of the sacrificiallayer and the reaction product film, a Cu wire embedded in the groovethrough the barrier film is obtained by removing the Cu layer from aportion located outside the groove so that the surface of the Cu layeris flush with the surface of a portion of the insulating layer locatedoutside the groove, for example.

Mn is used for forming the reaction product film, whereby the quantityof Mn contained in the Cu layer is reduced. Thus, the quantity of Mnremaining in the Cu wire consisting of the Cu layer can be reduced.

The sacrificial layer and the reaction product film are preferablyremoved by CMP. When CMP is employed for removing the sacrificial layerand the reaction product film, the sacrificial layer and the reactionproduct film can be removed through a single step. When the Cu layer isworked into the Cu wire by CMP continuously to the removal of thesacrificial layer and the reaction product film by CMP, a slurry forremoving a Ta (tantalum) film is employed, whereby the sacrificial layerand the reaction product film can be excellently removed, and the Culayer and the insulating layer can be removed at generally identicalpolishing rates. Consequently, a Cu wire having a surface excellent inplanarity can be obtained.

The sacrificial layer is preferably formed by PECVD (Plasma EnhancedChemical Vapor Deposition). In this case, a high temperature (about 400°C.) is applied to the Cu layer and the sacrificial layer stacked thereonin the process of stacking the sacrificial layer on the Cu layer,whereby no heat treatment (heat treatment after the stacking of thesacrificial layer) is required for forming the reaction product film onthe interface between the Cu layer and the sacrificial layer.Consequently, the steps of manufacturing the semiconductor device can besimplified.

The sacrificial layer is particularly preferably formed by PECVDemploying gas containing SiH₄ (silane). The sacrificial layer can beformed also by PECVD (TEOS-CVD) employing TEOS (Tetraethoxysilane). Inthe PECVD employing TEOS, however, O₂ gas is employed and the Cu layeretc. are exposed to an O₂ gas atmosphere of a high temperature (about400° C.), and hence Cu contained in the Cu layer is easily oxidized. Inthe PECVD employing the gas containing SiH₄, on the other hand, not theO₂ gas but N₂O gas is employed, whereby Cu is harder to oxidize ascompared with the PECVD employing TEOS.

After the formation of the barrier film, the steps of forming thereaction product film (stacking the sacrificial layer) and removing thesacrificial layer and the reaction product film may be carried out inthis order a plurality of times. When the steps are repeated a pluralityof times, the quantity of Mn contained in the Cu layer is reduced as thesteps are repeated. Therefore, the quantity of Mn remaining in the Cuwire can be reliably reduced.

A step of polishing the surface of the Cu layer by CMP is preferablyfurther carried out after the formation of the barrier film and beforethe stacking of the sacrificial layer. In the formation of the barrierfilm, Mn contained in the alloy film partially moves in the Cu layer, toappear on the surface of the Cu layer. When the surface of the Cu layeris polished by CMP to remove Mn appearing on the surface of the Cu layerand the sacrificial layer is thereafter stacked on the Cu layer, Mnremaining in the Cu layer is positively used for the reaction with Siand O. Consequently, the quantity of Mn contained in the Cu layer can beefficiently reduced, and the quantity of Mn remaining in the Cu wire canbe further reduced.

A method of manufacturing a semiconductor device according to a fourthaspect of the present invention includes the steps of: forming a groovein an insulating layer made of an insulating material containing Si andO; covering the inner surface of the groove with an alloy film made ofan alloy material containing Cu and Mn; stacking a Cu layer made of ametallic material mainly composed of Cu on the alloy film to fill up thegroove; stacking a sacrificial layer made of high-purity Cu on the Culayer; forming a barrier film made of MnSiO between the Cu layer and theinsulating layer by heat treatment after the stacking of the sacrificiallayer; and removing the sacrificial layer from the Cu layer after theformation of the barrier film.

According to the method, the groove is first formed in the insulatinglayer made of the insulating material containing Si and O. Then, theinner surface (the side surface and the bottom surface) of the groove iscovered with the alloy film made of the CuMn alloy. Thereafter the Culayer made of the metallic material mainly composed of Cu is formed onthe alloy film to fill up the groove. After the formation of the Culayer, the sacrificial layer made of high-purity Cu is stacked on the Culayer. After the formation of the sacrificial layer, the barrier filmmade of MnSiO is formed between the insulating layer and the Cu layer byheat treatment. After the heat treatment, the sacrificial layer isremoved from the Cu layer. After the removal of the sacrificial layer, aCu wire embedded in the groove through the barrier film is obtained byremoving the Cu layer from a portion located outside the groove so thatthe surface of the Cu layer is flush with the surface of a portion ofthe insulating layer located outside the groove, for example.

In the heat treatment, excess Mn not contributing to the formation ofthe barrier film diffuses into the Cu layer. The sacrificial layer madeof high-purity Cu is stacked on the Cu layer, whereby Mn diffusing intothe Cu layer partially moves in the Cu layer to be attracted to thesacrificial layer, and diffuses into the sacrificial layer. The quantityof Mn contained in the Cu layer is reduced due to the diffusion of Mninto the sacrificial layer. Therefore, the quantity of Mn remaining inthe Cu wire consisting of the Cu layer can be reduced.

The term “high-purity Cu” denotes Cu having purity of not less than99.995%.

A method of manufacturing a semiconductor device according to a fifthaspect of the present invention includes the steps of: forming a groovein an insulating layer made of an insulating material containing Si andO; covering the inner surface of the groove with an alloy film made ofan alloy material containing Cu and Mn; stacking a Cu layer made of ametallic material mainly composed of Cu on the alloy film to fill up thegroove; performing heat treatment after the stacking of the Cu layer;removing a surface layer portion of the Cu layer after the heattreatment; stacking a sacrificial layer made of a metallic materialmainly composed of Cu on the Cu layer after the removal of the surfacelayer portion of the Cu layer; reperforming heat treatment after thestacking of the sacrificial layer; and removing the sacrificial layerfrom the Cu layer after the reperformance of the heat treatment.

According to the method, the groove is first formed in the insulatinglayer made of the insulating material containing Si and O. Then, theinner surface (the side surface and the bottom surface) of the groove iscovered with the alloy film made of the CuMn alloy. Thereafter the Culayer made of the metallic material mainly composed of Cu is formed onthe alloy film to fill up the groove. After the stacking of the Culayer, the heat treatment is performed. The barrier film made of MnSiOis formed between the insulating layer and the Cu layer by the heattreatment. After the heat treatment, the surface layer portion of the Culayer is removed. Thereafter the sacrificial layer made of the metallicmaterial mainly composed of Cu is formed on the Cu layer, and the heattreatment is reperformed. After the sacrificial layer is removed fromthe Cu layer, a Cu wire embedded in the groove through the barrier filmis obtained by removing the Cu layer from a portion located outside thegroove so that the surface of the Cu layer is flush with the surface ofa portion of the insulating layer located outside the groove, forexample.

Excess Mn not contributing to the formation of the barrier film diffusesinto the Cu layer due to the heat treatment after the stacking of the Culayer. Mn diffusing into the Cu layer partially appears on the surfaceof the Cu layer. The surface layer portion of the Cu layer is removedafter the heat treatment, whereby Mn reaching the surface layer portionof the Cu layer and that appearing on the surface of the Cu layer areremoved along with the surface layer portion of the Cu layer. When thesacrificial layer is stacked after the surface layer portion of the Culayer is removed and the heat treatment is reperformed, Mn remaining inthe Cu layer diffuses into the sacrificial layer. The quantity of Mncontained in the Cu layer is reduced due to the diffusion of Mn into thesacrificial layer. Therefore, the quantity of Mn remaining in the Cuwire consisting of the Cu layer can be reduced.

In the method according to the fifth aspect, the sacrificial layer ispreferably made of high-purity Cu. When the sacrificial layer is made ofhigh-purity Cu, Mn remaining in the Cu layer can excellently diffuseinto the sacrificial layer. Consequently, the quantity of Mn containedin the Cu layer can be effectively reduced, and the quantity of Mnremaining in the Cu wire can be further reduced.

After the removal of the surface layer portion of the Cu layer, thesteps of stacking the sacrificial layer, reperforming the heat treatmentand removing the sacrificial layer may be repeated in this order aplurality of times. When the steps are repeated a plurality of times,the quantity of Mn contained in the Cu layer is reduced as the steps arerepeated. Therefore, the quantity of Mn remaining in the Cu wire can bereliably reduced.

The foregoing and other objects, features and effects of the presentinvention will become more apparent from the following detaileddescription of the embodiments with reference to the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view showing the structure of asemiconductor device manufactured by a method according to the presentinvention.

FIGS. 2A to 2G are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a firstembodiment of the present invention.

FIGS. 3A to 3G are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a secondembodiment of the present invention.

FIGS. 4A to 4G are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a thirdembodiment of the present invention.

FIGS. 5A to 5J are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a fourthembodiment of the present invention.

FIGS. 6A to 6H are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a fifthembodiment of the present invention.

FIGS. 7A to 7G are schematic sectional views showing the steps ofmanufacturing a semiconductor device by a method according to a sixthembodiment of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 is a schematic sectional view of a semiconductor devicemanufactured by a method according to an embodiment of the presentinvention.

A semiconductor device 1 includes a semiconductor substrate (not shown).Elements such as MOSFETs (Metal Oxide Semiconductor Field-EffectTransistors) are provided on the semiconductor substrate. A firstinsulating layer 2 made of SiO₂ is laminated on the semiconductorsubstrate.

A first groove 3 is formed in a surface layer portion of the firstinsulating layer 2 in a prescribed pattern. The first groove 3 is in theform of a recess dug from the upper surface of the first insulatinglayer 2. A first barrier film 4 made of MnSiO is formed on the innersurfaces (the side surfaces and the bottom surface) of the first groove3. A first Cu wire 5 made of a metallic material mainly composed of Cuis embedded in the first groove 3 through the first barrier film 4.

A second insulating layer 6 is stacked on the first insulating layer 2.The second insulating layer 6 has a structure obtained by stacking adiffusion preventing film 7, an interlayer dielectric film 8, an etchingstopper film 9 and an insulating film 10 in this order from the side ofthe first insulating layer 2.

The diffusion preventing film 7 is made of SiC (silicon carbide) and/orSiCN (silicon carbonitride), for example.

The interlayer dielectric film 8 and the insulating film 10 are made ofSiO₂ which is an insulating material containing Si and O, for example.

The etching stopper film 9 is made of SiC, for example.

A second groove 11 is formed in a surface layer portion of the secondinsulating layer 6. The second groove 11 is in the form of a recess dugfrom the upper surface of the insulating film 10 up to the upper surfaceof the interlayer dielectric film 8. The side surfaces of the secondgroove 11 are formed by the insulating film 10 and the etching stopperfilm 9, while the bottom surface of the second groove 11 is formed bythe upper surface of the interlayer dielectric film 8.

The second groove 11 is formed in a pattern having a portionintersecting with the first Cu wire 5 (the first groove 3) in plan view.In the portion where the first Cu wire 5 and the second groove 11intersect with each other in plan view, a via hole 12 passing throughthe diffusion preventing film 7 and the interlayer dielectric film 8 isformed between the first Cu wire 5 and the second groove 11.

A second barrier film 13 made of MnSiO is formed on the inner surfacesof the second groove 11 and the via hole 12 (the side surfaces and thebottom surface of the second groove 11 and the side surfaces of the viahole 12). A second Cu wire 14 and a via 15 made of a metallic materialmainly composed of Cu are embedded in the second groove 11 and the viahole 12 respectively through the second barrier film 13. The second Cuwire 14 and the via 15 are integrated with each other.

FIGS. 2A to 2G are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a firstembodiment of the present invention.

As shown in FIG. 2A, the diffusion preventing film 7, the interlayerdielectric film 8, the etching stopper film 9 and the insulating film 10are stacked in this order by CVD (Chemical Vapor Deposition) on thefirst insulating layer 2 having the first barrier film 4 and the firstCu wire 5 embedded therein. Thus, the second insulating layer 6 isformed on the first insulating layer 2.

Thereafter the second groove 11 and the via hole 12 are formed in thesecond insulating layer 6, as shown in FIG. 2B. More specifically, amask (not shown) having an opening selectively exposing a portion to beprovided with the via hole 12 is first formed on the second insulatinglayer 6. Then, the insulating film 10, the etching stopper film 9 andthe interlayer dielectric film 8 are dry-etched through the mask. Atthis time, the insulating film 10, the etching stopper film 9 and theinterlayer dielectric film 8 are continuously etched by switchingreaction gas (etchant) at proper timing. Then, the mask is removed fromthe second insulating layer 6, and another mask (not shown) having anopening selectively exposing a portion to be provided with the secondgroove 11 is formed on the second insulating layer 6. Then, theinsulating film 10 is dry-etched through the mask. Thereafter the secondgroove 11 and the via hole 12 are formed by removing exposed portions ofthe diffusion preventing film 7 and the etching stopper film 9.

Then, the overall surface of the second insulating layer 6 including theinner surfaces of the second groove 11 and the via hole 12 and a portionof the surface of the first Cu wire 5 facing the via hole 12 are coveredwith a metal film 21 made of MnO by sputtering, as shown in FIG. 2C. Themetal film 21 is formed with a thickness (1 to 10 nm, for example)necessary and sufficient for forming the second barrier film 13. At thistime, MnO in the metal film 21 is introduced into a portion of the metalfilm 21 in contact with the second insulating layer 6 (the overallsurface of the second insulating layer 6 including the inner surfaces ofthe second groove 11 and the via hole 12) due to the energy of thesputtering. Thus, Si and O in the second insulating layer 6 and MnO inthe metal film 21 are bonded to one another, whereby the barrier film 13made of MnSiO is formed on the overall surface of the second insulatinglayer 6 including the inner surfaces of the second groove 11 and the viahole 12. The portion of the metal film 21 in contact with the secondinsulating layer 6 disappears following the formation of the secondbarrier film 13, and the metal film 21 remains only on the first Cu wire5.

Thereafter hydrogen reduction is performed. The metal film 21 left onthe first Cu wire 5 is reduced by the hydrogen reduction, to be alteredto an Mn film 22 made of Mn, as shown in FIG. 2D. The hydrogen reductionmay be heat treatment in a hydrogen atmosphere or hydrogen plasmatreatment, for example.

Then, a seed film 23 made of a metallic material mainly composed of Cuis formed by sputtering to cover the overall surface of the secondbarrier film 13 and the surface of the Mn film 22, as shown in FIG. 2E.

Thereafter a plating layer 24 made of Cu is formed on the seed film 23by plating, as shown in FIG. 2F. The plating layer 24 is formed with athickness for filling up the via hole 12 and the second groove 11.

The plating layer 24 has a heterogeneous crystal structure and highspecific resistance in the state grown by plating. After the platinggrowth, therefore, heat treatment is performed for crystallizing(homogenizing the crystal structure of) the plating layer 24. At thistime, Mn in the Mn film 22 moves in the plating layer 24 and isdeposited on the surface of the plating layer 24, as shown in FIG. 2G.Therefore, the Mn film 22 disappears in the heat treatment forcrystallizing the plating layer 24.

Then, the plating layer 21 and the second barrier film 13 are polishedby CMP (Chemical Mechanical Polishing). The polishing is continued untilunnecessary portions of the plating layer 24 and the second barrier film13 formed outside the second groove 11 are entirely removed, the secondinsulating layer 6 (the insulating film 10) is exposed, and the exposedsurface of the second insulating layer 6 and the surface of the platinglayer 24 in the second groove 11 are flush with each other. Thus, thesemiconductor device 1 shown in FIG. 1 is obtained.

The metal film 21 made of MnO has relatively high adhesiveness to theinsulating film 10 made of SiO₂. Therefore, the metal film 21 hardlyseparates from the side surfaces of the second groove 11 (from theinsulating film 10) also when the same is formed with a small thicknessnecessary and sufficient for forming the second barrier film 13 with adesired thickness. Therefore, the second barrier film 13 can beexcellently formed on the inner surfaces of the second groove 11. Whenthe inner surfaces of the second groove 11 are covered with the metalfilm 21, the second barrier film 13 can be formed due to the energy ofthe sputtering, whereby no heat treatment may be performed for formingthe second barrier film 13.

O is removed from the portion of the metal film 21 in contact with thesurface of the first Cu wire 5 due to the hydrogen reduction, and theportion is reduced to the Mn film 22 made of Mn. The Mn film 22 diffusesinto the via 15 and the like, to disappear. Mn has higher electricalresistance than Cu. When the metal film 21 (the Mn film 22) is removedfrom the first Cu wire 5 in the aforementioned manner, therefore, theelectrical resistance between the first Cu wire 5 and the second Cu wire14 can be reduced as compared with a structure leaving the metal film 21made of MnO between the first Cu wire 5 and the via 15.

The plating layer 24 formed by plating growth has a heterogeneouscrystal structure and high specific resistance in the state grown byplating. The heat treatment for crystallizing the plating layer 24 isperformed after the formation of the plating layer 24 for homogenizing(crystallizing) the crystal structure of the plating layer 24, wherebythe specific resistance of the second Cu wire 14 and the via 15consisting of the plating layer 24 can be reduced.

FIGS. 3A to 3G are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a secondembodiment of the present invention.

As shown in FIG. 3A, the diffusion preventing film 7, the interlayerdielectric film 8, the etching stopper film 9 and the insulating film 10are stacked in this order by CVD (Chemical Vapor Deposition) on thefirst insulating layer 2 having the first barrier film 4 and the firstCu wire 5 embedded therein. Thus, the second insulating layer 6 isformed on the first insulating layer 2.

Thereafter the second groove 11 and the via hole 12 are formed in thesecond insulating layer 6, as shown in FIG. 3B. More specifically, amask (not shown) having an opening selectively exposing a portion to beprovided with the via hole 12 is first formed on the second insulatinglayer 6. Then, the insulating film 10, the etching stopper film 9 andthe interlayer dielectric film 8 are dry-etched through the mask. Atthis time, the insulating film 10, the etching stopper film 9 and theinterlayer dielectric film 8 are continuously etched by switchingreaction gas (etchant) at proper timing. Then, the mask is removed fromthe second insulating layer 6, and another mask (not shown) having anopening selectively exposing a portion to be provided with the secondgroove 11 is formed on the second insulating layer 6. Then, theinsulating film 10 is dry-etched through the mask. Thereafter the secondgroove 11 and the via hole 12 are formed by removing exposed portions ofthe diffusion preventing film 7 and the etching stopper film 9.

Then, the overall surface of the second insulating layer 6 including theinner surfaces of the second groove 11 and the via hole 12 and a portionof the surface of the first Cu wire 5 facing the via hole 12 are coveredwith a metal film 31 made of MnO by sputtering, as shown in FIG. 3C. Themetal film 31 is formed with a thickness (1 to 10 nm, for example)necessary and sufficient for forming the second barrier film 13. At thistime, MnO in the metal film 31 is introduced into a portion of the metalfilm 31 in contact with the second insulating layer 6 (the overallsurface of the second insulating layer 6 including the inner surfaces ofthe second groove 11 and the via hole 12) due to the energy of thesputtering. Thus, Si and O in the second insulating layer 6 and MnO inthe metal film 31 are bonded to one another, whereby the barrier film 13made of MnSiO is formed on the overall surface of the second insulatinglayer 6 including the inner surfaces of the second groove 11 and the viahole 12. The portion of the metal film 31 in contact with the secondinsulating layer 6 disappears following the formation of the secondbarrier film 13, and the metal film 31 remains only on the first Cu wire5.

Thereafter the metal film 31 left on the first Cu wire 5 is removed byreverse sputtering, as shown in FIG. 3D. More specifically, gasparticles (argon gas particles, for example) are collided with the metalfilm 31 from a generally vertical direction (a direction along thestacking direction of the second insulating layer 6), thereby removingthe portion of the metal film 31 formed on the first Cu wire 5. Thesecond barrier film 13 is strongly bonded to the second insulating layer6, and hence not removed by the reverse sputtering.

Then, a seed film 32 made of a metallic material mainly composed of Cuis formed by sputtering to cover the overall surface of the secondbarrier film 13 and a portion of the first Cu wire 5 exposed through thevia hole 12, as shown in FIG. 3E.

Thereafter a plating layer 33 made of Cu is formed on the seed film 32by plating, as shown in FIG. 3F. The plating layer 33 is formed with athickness for filling up the via hole 12 and the second groove 11.

Then, heat treatment is performed for crystallizing (homogenizing thecrystal structure of) the plating layer 33.

Then, the plating layer 33 and the second barrier film 13 are polishedby CMP. The polishing is continued until unnecessary portions of theplating layer 33 and the second barrier film 13 formed outside thesecond groove 11 are entirely removed, the second insulating layer 6(the insulating film 10) is exposed, and the exposed surface of thesecond insulating layer 6 and the surface of the plating layer 33 in thesecond groove 11 are flush with each other. Thus, the semiconductordevice 1 shown in FIG. 1 is obtained.

Also in the method according to the second embodiment, effects similarto those of the method (FIGS. 2A to 2G) according to the firstembodiment can be attained. According to the second embodiment, themetal film 31 left on the first Cu wire 5 is removed by the reversesputtering after the formation of the second barrier film 13. Thus, theelectrical resistance between the first Cu wire 5 and the second Cu wire14 can be reduced.

The reverse sputtering can be performed in a sputtering apparatusidentical to that employed for the sputtering. When the reversesputtering is employed for removing the portion of the metal film 31formed on the bottom surface of the via hole 12, therefore, the step ofpartially removing the metal film 31 can be carried out continuously tothe step of forming the metal film 31 in the same sputtering apparatus.Further, the step of forming the seed film 32 can be carried outcontinuously to the step of removing the metal film 31. Therefore, thestructure of an apparatus for manufacturing the semiconductor device 1can be simplified and a semiconductor wafer (a semiconductor substratein a wafer state provided with the insulating layers 2 and 6) may not betransported between the steps, whereby the time necessary formanufacturing the semiconductor device 1 can be reduced.

FIGS. 4A to 4G are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a thirdembodiment of the present invention.

As shown in FIG. 4A, the diffusion preventing film 7, the interlayerdielectric film 8, the etching stopper film 9 and the insulating film 10are stacked in this order by CVD on the first insulating layer 2 havingthe first barrier film 4 and the first Cu wire 5 embedded therein. Thus,the second insulating layer 6 is formed on the first insulating layer 2.

Thereafter the second groove 11 and the via hole 12 are formed in thesecond insulating layer 6, as shown in FIG. 4B. More specifically, amask (not shown) having an opening selectively exposing a portion to beprovided with the via hole 12 is first formed on the second insulatinglayer 6. Then, the insulating film 10, the etching stopper film 9 andthe interlayer dielectric film 8 are dry-etched through the mask. Atthis time, the insulating film 10, the etching stopper film 9 and theinterlayer dielectric film 8 are continuously etched by switchingreaction gas (etchant) at proper timing. Then, the mask is removed fromthe second insulating layer 6, and another mask (not shown) having anopening selectively exposing a portion to be provided with the secondgroove 11 is formed on the second insulating layer 6. Then, theinsulating film 10 is dry-etched through the mask. Thereafter the secondgroove 11 and the via hole 12 are formed by removing exposed portions ofthe diffusion preventing film 7 and the etching stopper film 9.

Then, the overall surface of the second insulating layer 6 including theinner surfaces of the second groove 11 and the via hole 12 and a portionof the first Cu wire 5 exposed through the via hole 12 are covered witha metal film 41 made of Mn by sputtering, as shown in FIG. 4C. The metalfilm 41 is formed with a thickness (1 to 10 nm, for example) necessaryand sufficient for forming the second barrier film 13 (see FIG. 1)having a desired thickness.

Thereafter heat treatment is performed for forming the second barrierfilm 13. The heat treatment is performed at a temperature of 250 to 350°C. for 20 to 60 minutes, for example. Mn in the metal film 41 is bondedto Si and O in the second insulating layer 6 on the interface betweenthe metal film 41 and the second insulating layer 6, due to the heattreatment. Consequently, the second barrier film 13 made of MnSiO isformed on the inner surfaces of the second groove 11 and the via hole12, as shown in FIG. 4D. The metal film 41 disappears following theformation of the second barrier film 13.

Then, a seed film 42 made of a metallic material mainly composed of Cuis formed by sputtering to cover the overall surface of the secondbarrier film 13 and the portion of the first Cu wire 5 exposed throughthe via hole 12, as shown in FIG. 4E. The seed film 42 is formed with athickness of 40 to 100 nm, for example.

Thereafter a plating layer 43 made of Cu is formed on the seed film 42by plating, as shown in FIG. 4F. The plating layer 43 is formed with athickness for filling up the via hole 12 and the second groove 11.

The plating layer 43 has a heterogeneous crystal structure and highspecific resistance in the state grown by plating. After the platinggrowth, therefore, heat treatment is performed for crystallizing(homogenizing the crystal structure of) the plating layer 43.

Then, the plating layer 43 and the second barrier film 13 are polishedby CMP. The polishing is continued until unnecessary portions of theplating layer 43 and the second barrier film 13 formed outside thesecond groove 11 are entirely removed, the second insulating layer 6(the insulating film 10) is exposed, and the exposed surface of thesecond insulating layer 6 and the surface of the plating layer 43 in thesecond groove 11 are flush with each other. Thus, the semiconductordevice 1 shown in FIG. 1 is obtained.

The metal film 41 made of Mn has relatively high adhesiveness to theinsulating film 10 made of SiO₂. Therefore, the metal film 41 hardlyseparates from the side surfaces of the second groove 11 (from theinsulating film 10) also when the same is formed with a small thicknessnecessary and sufficient for forming the second barrier film 13 with adesired thickness. Therefore, the second barrier film 13 can beexcellently formed on the inner surfaces of the second groove 11.

The metal film 41 is formed with a small thickness necessary andsufficient for forming the second barrier film 13 having the desiredthickness, whereby the quantity of excess Mn not contributing to theformation of the second barrier film 13 can be reduced. Consequently,the quantities of Mn remaining in the second Cu wire 14 and the via 15embedded in the second groove 11 and the via hole 12 respectivelythrough the second barrier film 13 can be reduced.

Thus, the quantities of Mn remaining in the second Cu wire 14 and thevia 15 can be reduced while the second barrier film 13 can beexcellently formed on the inner surfaces of the second groove 11.

Further, Cu is not present on and in the metal film 41 in the formationof the second barrier film 13, whereby no Cu spherically aggregates onthe second barrier film 13. Therefore, Cu can be excellently grown onthe second barrier film 13 by plating.

However, the plating layer 43 formed by the plating growth has aheterogeneous crystal structure and high specific resistance in thestate grown by plating. When the heat treatment for crystallizing theplating layer 43 is performed after the formation of the plating layer43, the crystal structure of the plating layer 43 can be homogenized,and the specific resistance of the plating layer 43 (the second Cu wire14) can be reduced.

FIGS. 5A to 5J are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a fourthembodiment of the present invention.

As shown in FIG. 5A, the diffusion preventing film 7, the interlayerdielectric film 8, the etching stopper film 9 and the insulating film 10are stacked in this order by CVD on the first insulating layer 2 havingthe first barrier film 4 and the first Cu wire 5 embedded therein. Thus,the second insulating layer 6 is formed on the first insulating layer 2.

Thereafter the second groove 11 and the via hole 12 are formed in thesecond insulating layer 6, as shown in FIG. 5B. More specifically, amask (not shown) having an opening selectively exposing a portion to beprovided with the via hole 12 is first formed on the second insulatinglayer 6. Then, portions (portions facing the opening) of the insulatingfilm 10, the etching stopper film 9 and the interlayer dielectric film 8exposed from the mask are successively removed by dry etching. At thistime, the insulating film 10, the etching stopper film 9 and theinterlayer dielectric film 8 are continuously etched by switchingreaction gas (etchant) at proper timing. Thereafter the mask is removedfrom the second insulating layer 6. Then, another mask (not shown)having an opening selectively exposing a portion to be provided with thesecond groove 11 is formed on the second insulating layer 6. Then, aportion (a portion facing the opening) of the insulating film 10 exposedfrom the mask is removed by dry etching. Thereafter the mask is removedfrom the second insulating layer 6. Then, exposed portions of thediffusion preventing film 7 and the etching stopper film 9 are removed.Thus, the second groove 11 and the via hole 12 are formed.

Then, the inner surfaces of the second groove 11 and the via hole 12 andthe overall upper surface of the second insulating layer 6 (theinsulating film 10) are covered with an alloy film 51 made of a CuMnalloy by sputtering, as shown in FIG. 5C.

Thereafter a seed film 52 made of a metallic material mainly composed ofCu is formed by sputtering to cover the overall surface of the alloyfilm 51, as shown in FIG. 5D.

Then, a Cu layer 53 made of a metallic material mainly composed of Cu isstacked on the seed film 52 by plating, as shown in FIG. 5E. The Culayer 53 is formed with a thickness for filling up the second groove 11and the via hole 12.

Thereafter heat treatment is performed. High heat is applied to thesecond insulating layer 6 and the alloy film 51, whereby Si and Ocontained in the second insulating layer 6 and Mn contained in the alloyfilm 51 react with (are bonded to) one another on the interface betweenthe second insulating layer 6 and the alloy film 51. Consequently, thesecond barrier film 13 made of MnSiO is formed between the secondinsulating layer 6 and the Cu layer 53, as shown in FIG. 5F. At thistime, excess Mn not contributing to the formation of the second barrierfilm 13 diffuses into the Cu layer 53, and partially appears on thesurface of the Cu layer 53. Further, the crystal structure of the Culayer 53 is homogenized and the specific resistance of the Cu layer 53(the second Cu wire 14) is reduced due to the heat treatment. The alloyfilm 51 disappears following the formation of the second barrier film13.

After the formation of the second barrier film 13, the surface of the Culayer 53 is polished by CMP. Mn is removed from the surface of the Culayer 53 along with the surface layer portion of the Cu layer 53 by thepolishing, as shown in FIG. 5G.

Then, a sacrificial layer 54 made of SiO₂ which is an insulatingmaterial containing Si and O is stacked on the Cu layer 53 by PECVD(Plasma Enhanced Chemical Vapor Deposition) employing gas containingSiH₄, as shown in FIG. 5H. In other words, the sacrificial layer 54consisting of a silane-based silicon oxide film is stacked on the Culayer 53. In the process of the stacking of the sacrificial layer 54, ahigh temperature (about 400° C.) is applied to the Cu layer 53 and thesacrificial layer 54 stacked thereon, whereby Si and O contained in thesacrificial layer 54 and Mn contained in the Cu layer 53 are bonded toone another on the interface between the Cu layer 53 and the sacrificiallayer 54, to form a reaction product film 55 made of MnSiO. Mn is usedfor the formation of the reaction product film 55, whereby the quantityof Mn contained in the Cu layer 53 is reduced. The sacrificial layer 54may be formed with a thickness (100 nm, for example) necessary andsufficient for forming the reaction product film 55.

Thereafter the sacrificial layer 54 and the reaction product film 55 areremoved by CMP, as shown in FIG. 5I.

As shown in FIG. 5J, a sacrificial layer 56 made of the same material asthat for the sacrificial layer 54 is stacked on the Cu layer 53 exposedby the removal of the sacrificial layer 54 and the reaction product film55. In other words, the sacrificial layer 56 made of SiO₂ is stacked byPECVD employing gas containing SiH₄. In the process of the stacking ofthe sacrificial layer 56, a high temperature (about 400° C.) is appliedto the Cu layer 53 and the sacrificial layer 56 stacked thereon, wherebySi and O contained in the sacrificial layer 56 and Mn contained in theCu layer 53 are bonded to one another, to form a reaction product film57 made of MnSiO. Mn is used for the formation of the reaction productfilm 57, whereby the quantity of Mn contained in the Cu layer 53 isfurther reduced. The sacrificial layer 56 may be formed with a thickness(100 nm, for example) necessary and sufficient for forming the reactionproduct film 57.

Thereafter the sacrificial layer 56 and the reaction product film 57 areremoved by CMP. Then, the Cu layer 53 and the second barrier film 13 arepolished by CMP. The polishing is continued until unnecessary portionsof the Cu layer 53 and the second barrier film 13 formed outside thesecond groove 11 are entirely removed, the upper surface of the secondinsulating layer 6 (the insulating film 10) is exposed, and the uppersurface of the second insulating layer 6 and that of the Cu layer 53 areflush with each other. Thus, the second Cu wire 14 embedded in thesecond groove 11 is formed, and the semiconductor device 1 shown in FIG.1 is obtained.

As hereinabove described, the sacrificial layer 54 made of theinsulating material containing Si and O is stacked on the Cu layer 53 byPECVD employing gas containing SiH₄. The sacrificial layer 54 containsSi and O, whereby the reaction product film 55 made of MnSiO is formedon the interface between the Cu layer 53 and the sacrificial layer 54 inthe process of the stacking of the sacrificial layer 54. Mn is used forthe formation of the reaction product film 55, whereby the quantity ofMn contained in the Cu layer 53 is reduced. Thus, the quantity of Mnremaining in the second Cu wire 14 consisting of the Cu layer 53 can bereduced.

After the removal of the sacrificial layer 54 and the reaction productfilm 55, the sacrificial layer 56 is stacked on the Cu layer 53 by PECVDemploying the gas containing SiH₄, and the reaction product film 57 madeof MnSiO is formed on the interface between the Cu layer 53 and thesacrificial layer 56. Thus, the quantity of Mn contained in the Cu layer53 is further reduced. Therefore, the quantity of Mn remaining in thesecond Cu wire 14 consisting of the Cu layer 53 can be further reduced.

According to PECVD, high heat is applied to the Cu layer 53 and thesacrificial layers 54 and 56 in the process of the stacking, and thereaction product films 55 and 57 are spontaneously formed. Therefore, noheat treatment (heat treatment after the stacking of the sacrificiallayers 54 and 56) is required for forming the reaction product films 55and 56. Thus, the manufacturing steps for the semiconductor device 1 canbe simplified as compared with a case of forming the sacrificial layers54 and 56 by a method other than PECVD.

The sacrificial layers 54 and 56 can also be formed by PECVD employingTEOS. According to PECVD employing TEOS, however, O₂ gas is employed andthe Cu layer 53 etc. are exposed to an O₂ gas atmosphere of a hightemperature (about 400° C.), and hence Cu contained in the Cu layer 53is easily oxidized. According to PECVD employing the gas containingSiH₄, on the other hand, not the O₂ gas but N₂O gas is employed, wherebyCu is harder to oxidize as compared with the PECVD employing TEOS.

The sacrificial layers 54 and 56 and the reaction product films 55 and57 are removed by CMP. Thus, the sacrificial layers 54 and 56 and thereaction product films 55 and 57 can be removed through single stepsrespectively. According to CMP employing a slurry for removing a Tafilm, the sacrificial layer 54 and the reaction product film 55 can beexcellently removed, and the Cu layer 53 and the second insulating layer6 can be removed at generally identical polishing rates continuously tothe removal of the sacrificial layer 54 and the reaction product film55. Consequently, the second Cu wire 14 can be obtained with a surfaceexcellent in planarity.

Further, the surface of the Cu layer 53 is polished by CMP after theformation of the second barrier film 13 and before the stacking of thesacrificial layer 54. In the formation of the second barrier film 13, Mncontained in the alloy film 51 partially moves in the Cu layer 53, andappears on the surface of the Cu layer 53. When the surface of the Culayer 53 is polished by CMP to remove Mn appearing on the surface of theCu layer 53 and the sacrificial layer 54 is thereafter stacked on the Culayer 53, Mn remaining in the Cu layer 53 is positively used for thereaction with Si and O. Consequently, the quantity of Mn contained inthe Cu layer 53 can be efficiently reduced, and the quantity of Mnremaining in the second Cu wire 14 can be further reduced.

If the quantity of Mn remaining in the Cu layer 53 can be sufficientlyreduced by the stacking of the sacrificial layer 54 and the formation ofthe reaction product film 55, the stacking of the sacrificial layer 56and the formation of the reaction product film 57 may be omitted.

After the formation of the reaction product film 57, the sacrificiallayer 56 and the reaction product film 57 may be removed and asacrificial layer made of an insulating material containing Si and O maybe formed on the Cu layer 53, so that a reaction product film made ofMnSiO is formed on the interface between the sacrificial layer and theCu layer 53. In other words, the steps of forming the reaction productfilm (stacking the sacrificial layer) and removing the sacrificial layerand the reaction product film may be repeated in this order not lessthan three times after the formation of the second barrier film 13. Whenthe steps are repeated a plurality of times, the quantity of Mncontained in the Cu layer 53 is reduced as the steps are repeated.Therefore, the quantity of Mn remaining in the second Cu wire 14 can bereliably reduced.

FIGS. 6A to 6H are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a fifthembodiment of the present invention.

As shown in FIG. 6A, the diffusion preventing film 7, the interlayerdielectric film 8, the etching stopper film 9 and the insulating film 10are stacked in this order by CVD on the first insulating layer 2 havingthe first barrier film 4 and the first Cu wire 5 embedded therein. Thus,the second insulating layer 6 is formed on the first insulating layer 2.

Thereafter the second groove 11 and the via hole 12 are formed in thesecond insulating layer 6, as shown in FIG. 6B. More specifically, amask (not shown) having an opening selectively exposing a portion to beprovided with the via hole 12 is first formed on the second insulatinglayer 6. Then, portions (portions facing the opening) of the insulatingfilm 10, the etching stopper film 9 and the interlayer dielectric film 8exposed from the mask are successively removed by dry etching. At thistime, the insulating film 10, the etching stopper film 9 and theinterlayer dielectric film 8 are continuously etched by switchingreaction gas (etchant) at proper timing. Thereafter the mask is removedfrom the second insulating layer 6. Then, another mask (not shown)having an opening selectively exposing a portion to be provided with thesecond groove 11 is formed on the second insulating layer 6. Then, aportion (a portion facing the opening) of the insulating film 10 exposedfrom the mask is removed by dry etching. Thereafter the mask is removedfrom the second insulating layer 6. Then, exposed portions of thediffusion preventing film 7 and the etching stopper film 9 are removed.Thus, the second groove 11 and the via hole 12 are formed.

Then, the inner surfaces of the second groove 11 and the via hole 12 andthe overall upper surface of the second insulating layer 6 (theinsulating film 10) are covered with an alloy film 61 made of a CuMnalloy by sputtering, as shown in FIG. 6C.

Thereafter a seed film 62 made of a metallic material mainly composed ofCu is formed by sputtering to cover the overall surface of the alloyfilm 61, as shown in FIG. 6D.

Then, a Cu layer 63 made of a metallic material mainly composed of Cu isstacked on the seed film 62 by plating, as shown in FIG. 6E. The Culayer 63 is formed with a thickness for filling up the second groove 11and the via hole 12.

After the stacking of the Cu layer 63, a sacrificial layer 64 made ofhigh-purity Cu (Cu having purity of not less than 99.995%, preferablynot less than 99.9999%) is staked on the Cu layer 63 by sputtering, asshown in FIG. 6F.

Thereafter heat treatment is performed. High heat is applied to thesecond insulating layer 6 and the alloy film 61, whereby Si and Ocontained in the second insulating layer 6 and Mn contained in the alloyfilm 61 are bonded to one another on the interface between the secondinsulating layer 6 and the alloy film 61. Consequently, the secondbarrier film 13 made of MnSiO is formed between the second insulatinglayer 6 and the Cu layer 63, as shown in FIG. 6G. Further, the crystalstructure of the Cu layer 63 is homogenized and the specific resistanceof the Cu layer 63 (the second Cu wire 14) is reduced due to the heattreatment. The alloy film 61 disappears following the formation of thesecond barrier film 13.

In the heat treatment, excess Mn not contributing to the formation ofthe second barrier film 13 diffuses into the Cu layer 63. Thesacrificial layer 64 made of high-purity Cu is stacked on the Cu layer63, whereby Mn diffusing into the Cu layer 63 partially moves in the Culayer 63 to be attracted to the sacrificial layer 64, and diffuses intothe sacrificial layer 64. Mn diffusing into the sacrificial layer 64partially appears on the surface of the sacrificial layer 64.

After the heat treatment, the sacrificial layer 64 is removed from theCu layer 63 by CMP, as shown in FIG. 6H. Then, the Cu layer 63 and thesecond barrier film 13 are polished by CMP. The polishing is continueduntil unnecessary portions of the Cu layer 63 and the second barrierfilm 13 formed outside the second groove 11 are entirely removed, theupper surface of the second insulating layer 6 (the insulating film 10)is exposed, and the upper surface of the second insulating layer 6 andthat of the Cu layer 63 are flush with each other. Thus, the second Cuwire 14 embedded in the second groove 11 is formed, and thesemiconductor device 1 shown in FIG. 1 is obtained.

As hereinabove described, the sacrificial layer 64 made of high-purityCu is stacked on the Cu layer 63 after the formation of the Cu layer 63.After the formation of the sacrificial layer 64, the second barrier film13 made of MnSiO is formed between the Cu layer 63 and the secondinsulating layer 6 by the heat treatment. At this time, excess Mn notcontributing to the formation of the second barrier film 13 diffusesinto the Cu layer 63. The sacrificial layer 64 made of high-purity Cu isstacked on the Cu layer 63, whereby Mn diffusing into the Cu layer 63partially moves in the Cu layer 63 to be attracted to the sacrificiallayer 64, and diffuses into the sacrificial layer 64. The quantity of Mncontained in the Cu layer 63 is reduced due to the diffusion of Mn intothe sacrificial layer 64. Therefore, the quantity of Mn remaining in thesecond Cu layer 14 consisting of the Cu layer 63 can be reduced.

FIGS. 7A to 7G are schematic sectional views showing the steps ofmanufacturing the semiconductor device by a method according to a sixthembodiment of the present invention.

The steps shown in FIGS. 7A to 7G are carried out after the steps shownin FIGS. 6A to 6E, in place of the steps shown in FIGS. 6F to 6H.

After the Cu layer 63 is stacked in the step shown in FIG. 6E, heattreatment is performed. High heat is applied to the second insulatinglayer 6 and the alloy film 61, whereby Si and O contained in the secondinsulating layer 6 and Mn contained in the alloy film 61 are bonded toone another on the interface between the second insulating layer 6 andthe alloy film 61. Consequently, the second barrier film 13 made ofMnSiO is formed between the second insulating layer 6 and the Cu layer63, as shown in FIG. 7A. At this time, excess Mn not contributing to theformation of the second barrier film 13 moves in the Cu layer 63, andpartially appears on the surface of the Cu layer 63. Further, thecrystal structure of the Cu layer 63 is homogenized and the specificresistance of the Cu layer 63 (the second Cu wire 14) is reduced due tothe heat treatment. The alloy film 61 disappears following the formationof the second barrier film 13.

After the heat treatment, the surface of the Cu layer 63 is polished byCMP. Mn contained in the surface layer portion of the Cu layer 63 andthat appearing on the surface of the Cu layer 63 are removed along withthe surface layer portion of the Cu layer 63 due to the polishing, asshown in FIG. 7B.

Then, a sacrificial layer 71 made of high-purity Cu is stacked on the Culayer 63 by sputtering, as shown in FIG. 7C.

Thereafter heat treatment is performed. Mn contained in the Cu layer 63partially moves in the Cu layer 63 to be attracted to the sacrificiallayer 71 and diffuses into the sacrificial layer 71 due to the heattreatment, as shown in FIG. 7D. Mn diffusing into the sacrificial layer71 partially appears on the surface of the sacrificial layer 71.

After the heat treatment, the sacrificial layer 71 is removed from theCu layer 63 by CMP, as shown in FIG. 7E. Thus, Mn diffusing into thesacrificial layer 71 is removed along with the sacrificial layer 71.

Then, a sacrificial layer 72 made of high-purity Cu is stacked on the Culayer 63 by sputtering, as shown in FIG. 7F.

Thereafter heat treatment is reperformed. Mn still remaining in the Culayer 63 partially moves in the Cu layer 63 to be attracted to thesacrificial layer 72 and diffuses into the sacrificial layer 72 due tothe heat treatment, as shown in FIG. 7G. Mn diffusing into thesacrificial layer 72 partially appears on the surface of the sacrificiallayer 72.

After the heat treatment, the sacrificial layer 72 is removed from theCu layer 63. Then, the Cu layer 63 and the second barrier film 13 arepolished by CMP. The polishing is continued until unnecessary portionsof the Cu layer 63 and the second barrier film 13 formed outside thesecond groove 11 are entirely removed, the upper surface of the secondinsulating layer 6 (the insulating film 10) is exposed, and the uppersurface of the second insulating layer 6 and that of the Cu layer 63 areflush with each other. Thus, the second Cu wire 14 embedded in thesecond groove 11 is formed, and the semiconductor device 1 shown in FIG.1 is obtained.

According to the method, the heat treatment is performed after thestacking of the Cu layer 63. The second barrier film 13 made of MnSiO isformed between the second insulating layer 6 and the Cu layer 63 due tothe heat treatment. After the heat treatment, the surface layer portionof the Cu layer 63 is removed. Thereafter the sacrificial layer 71 madeof high-purity Cu is formed on the Cu layer 63, and the heat treatmentis reperformed.

Excess Mn not contributing to the formation of the second barrier film13 diffuses into the Cu layer 63 due to the heat treatment after thestacking of the Cu layer 63. Mn diffusing into the Cu layer 63 partiallyappears on the surface of the Cu layer 63. The surface layer portion ofthe Cu layer 63 is removed after the heat treatment, whereby Mn reachingthe surface portion of the Cu layer 63 and that appearing on the surfaceof the Cu layer 63 are removed along with the surface layer portion ofthe Cu layer 63. When the sacrificial layer 71 is stacked after thesurface layer portion of the Cu layer 63 is removed and the heattreatment is reperformed, Mn remaining in the Cu layer 63 diffuses intothe sacrificial layer 71. The quantity of Mn contained in the Cu layer63 is reduced due to the diffusion of Mn into the sacrificial layer 71.Therefore, the quantity of Mn remaining in the second Cu wire 14consisting of the Cu layer 63 can be reduced.

After the removal of the sacrificial layer 71, the sacrificial layer 72made of high-purity Cu is formed on the Cu layer 63, and the heattreatment is further reperformed. Mn remaining in the Cu layer 63diffuses into the sacrificial layer 72 due to the heat treatment. Thequantity of Mn contained in the Cu layer 63 is further reduced due tothe diffusion of Mn into the sacrificial layer 72. Thus, the quantity ofMn remaining in the second Cu wire 14 consisting of the Cu layer 63 canbe further reduced.

The material for the sacrificial layers 71 and 72 is not restricted tothe high-purity Cu, but may be prepared from Cu having lower purity thanthe high-purity Cu. If the sacrificial layers 71 and 72 are made of thehigh-purity Cu, however, Mn remaining in the Cu layer 63 can excellentlydiffuse into the sacrificial layers 71 and 72. Consequently, thequantity of Mn contained in the Cu layer 63 can be effectively reduced,and the quantity of Mn remaining in the second Cu wire 14 can be furtherreduced.

If the quantity of Mn remaining in the Cu layer 63 can be sufficientlyreduced by the stacking of the sacrificial layer 71, the heat treatmentand the removal of the sacrificial layer 71, the stacking of thesacrificial layer 72, the heat treatment and the removal of thesacrificial layer 72 may be omitted.

After the removal of the sacrificial layer 72, stacking of a sacrificiallayer made of a metallic material mainly composed of Cu, heat treatmentand removal of the sacrificial layer may be additionally performed. Inother words, the steps of stacking the sacrificial layer, performing theheat treatment and removing the sacrificial layer may be repeated inthis order not less than three times after the removal of the surfacelayer portion of the Cu layer 63. When the steps are repeated aplurality of times, the quantity of Mn contained in the Cu layer 63 isreduced as the steps are repeated. Therefore, the quantity of Mnremaining in the second Cu wire 14 can be reliably reduced.

While a method of forming the first barrier film 4 and the first Cu wire5 has not been described, the first barrier film 4 and the first Cu wire5 can be formed by a method similar to that for forming the secondbarrier film 13 and the second Cu wire 14.

In a first method, for example, the first groove 3 in the form of therecess dug from the surface of the first insulating layer 2 is formed inthe first insulating layer 2 by photolithography and etching, and analloy film made of a MnO is formed on the side surfaces and the bottomsurface of the first groove 3 by sputtering. At this time, Si and O inthe first insulating layer 2 and MnO in the metal film are bonded to oneanother due to the energy of the sputtering, whereby the first barrierfilm 4 made of MnSiO is formed on the side surfaces and the bottomsurface of the first groove 3. Then, a seed film and a Cu layer bothmade of a metallic material mainly composed of Cu are successivelyformed by plating. Then, unnecessary portions (portions formed outsidethe first groove 3) of the plating layer are removed by CMP. Thus, thefirst barrier film 4 and the first wire 5 are obtained in the firstgroove 3.

In a second method, the first groove 3 in the form of the recess dugfrom the surface of the first insulating layer 2 is formed in the firstinsulating layer 2 by photolithography and etching, and a metal filmmade of a Mn is formed on the side surfaces and the bottom surface ofthe first groove 3 by sputtering. Then, heat treatment is performed,whereby the first barrier film 4 made of MnSiO is formed on the sidesurfaces and the bottom surface of the first groove 3. Then, a seed filmand a Cu layer both made of a metallic material mainly composed of Cuare successively formed by plating. Then, unnecessary portions (portionsformed outside the first groove 3) of the plating layer are removed byCMP. Thus, the first barrier film 4 and the first wire 5 are obtained inthe first groove 3.

In a third method, the first groove 3 in the form of the recess dug fromthe surface of the first insulating layer 2 is formed in the firstinsulating layer 2 by photolithography and etching, and an alloy filmmade of a CuMn alloy is formed on the side surfaces and the bottomsurface of the first groove 3 by sputtering. Then, a seed film and a Culayer both made of a metallic material mainly composed of Cu aresuccessively formed by plating. Then, a sacrificial layer made of aninsulating material containing Si and O is stacked on the Cu layer and areaction product film made of MnSiO on the interface between thesacrificial layer and the Cu layer. After removal of the sacrificiallayer and the reaction product film, the Cu layer and the first barrierfilm 4 are removed from portions formed outside the first groove 3 sothat the surface of the Cu layer is flush with the surface of theinsulating layer located outside the first groove 3, for example,whereby the first Cu wire 5 embedded in the first groove 3 through thefirst barrier film 4 is obtained.

In a forth method, the first groove 3 in the form of the recess dug fromthe surface of the first insulating layer 2 is formed in the firstinsulating layer 2 by photolithography and etching, and an alloy filmmade of a CuMn alloy is formed on the side surfaces and the bottomsurface of the first groove 3 by sputtering. Then, a seed film and a Culayer both made of a metallic material mainly composed of Cu aresuccessively formed by plating. Then, a sacrificial layer made ofhigh-purity Cu is stacked on the Cu layer. After the formation of thesacrificial layer, heat treatment is performed. After the heattreatment, the sacrificial layer is removed from the Cu layer. After theremoval of the sacrificial layer, the Cu layer and the first barrierfilm 4 are removed from portions formed outside the first groove 3 sothat the surface of the Cu layer is flush with the surface of theinsulating layer located outside the first groove 3, for example,whereby the first Cu wire 5 embedded in the first groove 3 through thefirst barrier film 4 is obtained.

The material for the interlayer dielectric film 8 and the insulatingfilm 10 may simply be an insulating material containing Si and O, andSiOC (carbon-doped silicon oxide) or SiOF (fluorine-doped silicon oxide)can be employed as the material for the interlayer dielectric film 8 andthe insulating film 10, in place of SiO₂.

While the present invention is applied to the method of manufacturingthe semiconductor device having the first Cu wire 5 and the second Cuwire 14 made of the metallic material mainly composed of Cu, the presentinvention is also applicable to a method of manufacturing a capacitorhaving an electrode made of a metallic material mainly composed of Cu inan insulating layer containing Si and O.

While the present invention has been described in detail by way of theembodiments thereof, it should be understood that these embodiments aremerely illustrative of the technical principles of the present inventionbut not limitative of the invention. The spirit and scope of the presentinvention are to be limited only by the appended claims.

This application corresponds to Japanese Patent Application No.2008-202138 filed with the Japan Patent Office on Aug. 5, 2008, JapanesePatent Application No. 2008-214626 filed with the Japan Patent Office onAug. 22, 2008, Japanese Patent Application No. 2008-236649 filed withthe Japan Patent Office on Sep. 16, 2008 and Japanese Patent ApplicationNo. 2008-245864 filed with the Japan Patent Office on Sep. 25, 2008, thedisclosures of these applications are incorporated herein by reference.

1. A method of manufacturing a semiconductor device, comprising: aninsulating layer forming step of forming; a groove forming step offorming a groove in an insulating layer made of an insulating materialcontaining Si and O; a metal film applying step of covering the innersurface of the groove with a metal film made of MnO_(x) (x: a numbergreater than zero) or Mn; a barrier film forming step of forming abarrier film made of Mn_(x)Si_(y)O_(z) (x, y and z: numbers greater thanzero) on the inner surface of the groove; and a wire forming step offorming a Cu wire made of a metallic material mainly composed of Cu onthe metal film.
 2. The method of manufacturing a semiconductor deviceaccording to claim 1, wherein the metal film made of MnO_(x) is formedby sputtering in the metal film applying step, and the barrier filmforming step is the same as the metal film applying step.
 3. The methodof manufacturing a semiconductor device according to claim 2, wherein alower wire electrically connected with the Cu wire is formed under theinsulating layer, the method further comprises: a via hole forming stepof forming a via hole extending from the groove toward the lower wireand passing through the insulating layer in the thickness directionafter the groove forming step and before the metal film applying step,and a via forming step of forming a via made of a metallic materialmainly composed of Cu in the via hole after the metal film applyingstep, and the side surface of the via hole and a portion of the surfaceof the lower wire facing the via hole are also covered with the metalfilm in the metal film applying step, in addition to the inner surfaceof the groove.
 4. The method of manufacturing a semiconductor deviceaccording to claim 3, further comprising a step of removing O from aportion of the metal film in contact with the surface of the lower wireby hydrogen reduction in advance of the via forming step.
 5. The methodof manufacturing a semiconductor device according to claim 3, furthercomprising a step of selectively removing a portion of the metal film incontact with the surface of the lower wire by reverse sputtering inadvance of the via forming step.
 6. The method of manufacturing asemiconductor device according to claim 2, wherein the wire forming stepincludes the steps of: forming a seed film made of a metallic materialmainly composed of Cu on the metal film by sputtering, and forming aplating layer made of Cu on the seed film by plating.
 7. The method ofmanufacturing a semiconductor device according to claim 6, wherein thewire forming step further includes a crystallizing step of crystallizingthe plating layer by heat treatment.
 8. The method of manufacturing asemiconductor device according to claim 1, wherein the metal film madeof Mn is formed in the metal film applying step, and heat treatment isperformed in the barrier film forming step after the metal film applyingstep.
 9. The method of manufacturing a semiconductor device according toclaim 8, wherein the wire forming step includes the steps of: forming aseed film made of a metallic material mainly composed of Cu on thebarrier film by sputtering, and forming a plating layer made of Cu onthe seed film by plating.
 10. The method of manufacturing asemiconductor device according to claim 9, wherein the wire forming stepfurther includes a crystallizing step of crystallizing the plating layerby heat treatment.
 11. A method of manufacturing a semiconductor device,comprising the steps of: forming a groove in an insulating layer made ofan insulating material containing Si and O; covering the inner surfaceof the groove with an alloy film made of an alloy material containing Cuand Mn; stacking a Cu layer made of a metallic material mainly composedof Cu on the alloy film to fill up the groove; forming a barrier filmmade of Mn_(x)Si_(y)O_(z) (x, y and z: numbers greater than zero)between the Cu layer and the insulating layer by heat treatment;stacking a sacrificial layer on the Cu layer; and removing thesacrificial layer from the Cu layer after formation of the barrier film.12. The method of manufacturing a semiconductor device according toclaim 11, wherein the sacrificial layer made of an insulating materialcontaining Si and O on the Cu layer for forming a reaction product filmmade of Mn_(x)Si_(y)O_(z) on the Cu layer after the formation of thebarrier film in the step of stacking the sacrificial layer; and removingthe sacrificial layer and the reaction product film from the Cu layer inthe step of removing the sacrificial layer.
 13. The method ofmanufacturing a semiconductor device according to claim 12, furthercomprising a step of polishing the surface of the Cu layer by chemicalmechanical polishing after the formation of the barrier film and beforethe stacking of the sacrificial layer.
 14. The method of manufacturing asemiconductor device according to claim 12, wherein the sacrificiallayer and the reaction product film are removed by chemical mechanicalpolishing.
 15. The method of manufacturing a semiconductor deviceaccording to claim 12, wherein the sacrificial layer is stacked byplasma chemical vapor deposition.
 16. The method of manufacturing asemiconductor device according to claim 15, wherein the sacrificiallayer is stacked by plasma chemical vapor deposition employing gascontaining SiH₄.
 17. The method of manufacturing a semiconductor deviceaccording to claim 12, wherein the steps of stacking the sacrificiallayer and removing the sacrificial layer and the reaction product filmare carried out in this order a plurality of times after the formationof the barrier film.
 18. The method of manufacturing a semiconductordevice according to claim 11, wherein the sacrificial layer is made ofhigh-purity Cu, and the step of forming the barrier film is carried outafter the stacking of the sacrificial layer.
 19. The method ofmanufacturing a semiconductor device according to claim 11, wherein heattreatment is performed in the step of forming the barrier film after thestacking of the Cu layer; a step of removing a surface layer portion ofthe Cu layer is carried out after the heat treatment; the sacrificiallayer is made of a metallic material mainly composed of Cu and stackedon the Cu layer after the removal of the surface layer portion of the Culayer; a step of reperforming heat treatment is carried out after thestacking of the sacrificial layer; and a step of removing thesacrificial layer from the Cu layer after the reperformance of the heattreatment.
 20. The method of manufacturing a semiconductor deviceaccording to claim 19, wherein the sacrificial layer is made ofhigh-purity Cu.
 21. The method of manufacturing a semiconductor deviceaccording to claim 19, wherein the steps of stacking the sacrificiallayer, reperforming the heat treatment and removing the sacrificiallayer are repeated in this order a plurality of times after the removalof the surface layer portion of the Cu layer.